Isolation and Characterization of the Free Phenylphosphinidene Chalcogenides C(6)H(5)P=O and C(6)H(5)P=S, the Phosphorous Analogues of Nitrosobenzene and Thionitrosobenzene

The structures and reactivities of organic phosphinidene chalcogenides have been mainly inferred from trapping or complexation experiments. Phosphinidene chalcogenide derivatives appear to be an elusive family of molecules that have been suggested as reactive intermediates in multiple organophosphorus reactions. The quest to isolate “free” phosphinidene chalcogenides remains a challenge in the field. Here, we present the synthesis, IR, and UV/Vis spectroscopic identification of hitherto elusive phenylphosphinidene oxide and phenylphosphinidene sulfide from the corresponding phosphonic diazide precursors. We isolated these higher congeners of nitroso‐ and thionitrosobenzene in argon matrices at 10 K. The spectral assignments are supported by B3LYP/6–311++G(3df,3pd) and MP2/cc‐pVTZ computations.